Synthesis of Hetero Cycles and New Organic Compounds from (Azo, Imine, Sugars).

 

Raja, Abed Alameer, Gafel

Chemistry Department, Education College, Kufa University, Iraq

*Corresponding Author E-mail: dr.nagham_mj@yahoo.com

 

 

ABSTRACT:

This study involved, preparation of many hetero cycles (thiazine, diazine, imidazolone ) and other organic compounds via coupling of (azo compounds, imine compounds, sugars).

 

These compounds synthesized via reaction .between any di amine compounds (methyleudiamine ,phenylen di amine) with sugars (xylose, ribose, arabinose) to form imines compounds which react with (azo compounds, o-anthranilicacide,thiol benzoic acid, Glycine )to give new organic compounds [1-13] which characterized by several techniques (FT.IR, H.NMR, C.H.N) and melting points .

 

KEY WORDS: bis-cycles, diazine.

 

INTRODUCTION:

The cycles containing (S, N) in there structure which incorporate with azo compounds or imine compounds are increase of applications of these compounds in several fields(1-3), the importance of such compounds lies in their diverse pharmaceutical activities as anti microbial.

 

Azo compounds and I mine compounds act staring materials to synthesis and formation new organic compounds such as (thiazine, diazine, imidazolone, five, six, seven –membered ring )(4-7)

 

I mine –sugar compounds have found to be an important moiety in creation of Novel medical materials. Many cycles containing (sulfur and Nitvoger in their structures were found in natural products like penicillin drug, most of thiazine cycles have pharmacological interest due to their activity of the central nervous system, as enzyme inhibitors, anticonvulsant, and other applications(8-12).

 

EXPERIMENTAL:

All chemical materials in purity 99.8%, FT.IR-spectra were recorded on Shimadzu 8300, KBr –disk., H.NMR –spectra and (C.H.N) –analyzer were recorded in Malaysia, the melting points were recorded by electro thermal 9300 LTD, UK.

 

Synthesis of compounds [1-2]:

2-amino thiophene (0.01mole ) dissolved in (2)ml of hydrochloric acid with sodium nitrite at (0-5)C̊ to give compound [1], which reacted with (0.01mole) in basic medium of sodium hydroxide.(10%) with stir, the precipitate filtered and recrystallized to give 85% of compounds [2].

 

Synthesis of compounds [3-6]:

According to procedure(12, 13), a mixture.of compound [2] (0.01mole) reacted with one of (0.01mole) of hydrazine, 0.01mole of 0-phenylene di amine, 0.02mole of 0-phenylene di amine ) in presence of absolute ethanol under reflux for (4hrs), the precipitate filtered to yield (82, 85, 88) % of compounds [3-5] respectively.(0.01mole) of compound [5] reacted with (0.02mole) of ribose sugar under reflux for (3hrs) in presence of absolute ethanol to yield 87% of compound [6].

 

Synthesis of compounds [7-10] :

These compounds synthesized according to study(13), (0.01mole) of p-phenylene di amine reacted with (0.02mole) of xylose sugar under reflux for (3hrs) in presence of absolute ethanol to yield 83% of compound [7], which (0.01mole) reacted with (0.02mole) from one of (Glycine, 0-thiol benzoic acid, 0-anthranilic acid) under reflux for (5hrs) in presence of drug benzene to yield (84, 82, 87) % of compound [8-10] respectively.

 

 

Scheme (1):                                                                 

 

Scheme (2):

 

 

Scheme (3):

 

 

Synthesis of compounds [11-13]:

To synthesis of these compounds, (0.01mole) of methylene di amine reacts with (0.02mole) of arabinose sugar under reflux for (3hrs) in presence of absolute ethanol, the precipitate filtered recrystallized to give 85% from compound [11], which reacted with one of (benzaldehyde, thiophenediazonium) in basic medium of sodium hydroxide in presence of ethanol as a solvent in stir for (4hrs), the precipitate filtered and dried, recrystalized to yield (87, 89)% of compounds [12-13] respectively.

 

RESULTS AND DISCUSSION :

This study involed, synthesis of new compounds started from coupling reaction of thiophendiazonium with malonic acid in base medium, then these compounds reacts with di amine compounds to yield.(five, six, seven ) –membered ring from hetero cyclic compounds, some products of these reactions give amine –sugar compounds, and other products of these rections produce. azo –amine compounds with sugars such as compounds [6, 13].

 

The synthesized compounds [2-13] characterized by I.R –spectra, H.NMR –spectra, (C.H.N) –analysis, and melting points.

Table (1):FT.IR –data (cm-1) of compounds [2-13]

Comp.

No.

(( Only important frequency)).

(-N=N-) azo

(-CO-)of amide

(-NH-)of amide

(CH=N) imine

Others groups

[2]

1480

 /

 /

 /

(COOH)carbonyl of carboxyl:1735

[3]

1492

1689

3280

 /

(CH) aliphatic:2978

[4]

1490

1696

3317

 /

(CH)aliphatic:2980

[5]

1487

1680

3230

 /

(NH2) amine: 3360

[6]

1498

1695

3255

1620

(OH) :3410

[7]

 /

 /

 /

1636

(OH) :3435

[8]

 /

1686

 /

 /

(NH)of cycle:3270; (OH):3422

[9]

 /

1696

 /

 /

(OH):3428; (CH-S):1404

[10]

 /

1690

 /

 /

(NH) of cycle:3260; (OH) :3430

[11]

 /

 /

 /

1637

(OH) :3317

[12]

 /

 /

 /

1630

(OH) :3420; (CH=C) :3095

[13]

1486

 /

 /

1638

(OH) :3312

 

Table (2) :1H.NMR (ppm) of some compounds

Comp.

No.

H.NMR ((DMSO)) ((only important peaks)).

(CH=N) amine

(OH) of sugar

Other peaks

[6]

8.87

(3.7-5)

9.98 (NH)proton of amide, 3.5 (CH-N=N-).

[9]

 /

(3.9-4.8)

3.4(S-CH-N) proton of thiazine cycle

[10]

 /

(3.5-4.6)

5.5 (NH-CH-N) proton of diazine cycle

[11]

8.89

(3.65-4.95)

3.30 (-N-CH2-N-).

[13]

8.86

(3.7-4.98)

3.45 (-N-CH-N).

 

Table (3) :physical properties and(C.H.N)-analysis of compound [2-13]

Comp. No.

M.F

m.p (+2)C̊

Nameof compounds

Calc./found

%C

%H

%N

[2]

C7H6N2O4S

172

2-(2-thiophene azo)malonic acid

39.25

39.08

2.80

2.65

13.08

13.00

[3]

C7H6N4O2S

189

4-(2-thiophene azo)-3, 5-di one-diazolidine

40.0

39.83

2.85

2.71

26.66

26.51

[4]

C13H10N14O2S

200

6-(2-thiophene–azo)-5, 7-di one -2, 3-benzo diazepane

54.54

54.35

3.49

3.33

19.58

19.28

[5]

C19H18N6O2S

205

2-(2-thiophene–azo)-1, 3- bis(1, 2-phenylene di amine)-propyl -1, 3-di one

57.86

57.67

4.56

4.37

21.31

21.16

[6]

C29H34N6O10S

218

2-(2-thiophene–azo)-1, 3-bis(1-amino-2-riboselidine)propyl-1, 3-dione

52.88

52.52

5.16

5.06

12.76

12.45

[7]

C16H24N2O8

160

1, 4-Bis(xylose–amine)benzene

51.61

51.42

6.45

6.21

7.52

7.30

[8]

C20H30N4O10

248

1, 4-bis(2-xylose-5-one-1, 3- di azolidine )benzene

49.38

49.20

6.17

6.04

11.52

11.31

[9]

C30H32N2O10S2

271

1, 4-bis(2-xylose-4-one-5, 6-benzo thiazine )benzene

55.90

55.74

4.96

4.70

4.34

4.19

[10]

C30H34N4O10

256

1, 4-bis(2-xylose-6-one-4, 5-benzo diazine)benzene

59.01

58.90

5.57

5.31

9.18

9.02

[11]

C11H22N2O8

148

1, 1-bis(arabinose-amine)methylene

42.58

42.27

7.09

7.00

9.03

8.92

[12]

C18H26N2O8

173

2, 2-bis(arabinose-amine)styrene

54.27

57.12

6.53

6.26

7.03

6.85

[13]

C15H24N4O8S

181

2-bis(arabinose amine)thiopheneazo

42.85

42.57

5.71

5.63

13.33

13.20

 

In I.R spectra :appearance absorption bands at (1480-1498) cm-1 due to azo group(15, 16) (-N=N-)in compounds [2-6, 13], absorption bands at (1680-1696)cm-1 due to carbonyl group of amide (-CO-NH-) in cyclic compounds [3-6, 8-10] absorption bands at (3230-3317) cm-1 due to (-NH) of amide(12) in compounds [3-6] absorption bands at (1620-1638) cm-1 due to amine group(13) (CH=N) in compounds [6, 7, 11-13], and other bands are summarized in table (1) and figures (1-4).

 

 

The H.NMR –spectra, showed peaks at and (8.86 -8.89) due to proton of amine group(14) (CH=N) in compounds [6, 11, 13] peaks at and (3.5 -5) due to proton of hydroxyl groups of sugars (-OH) in compounds [6, 9 -13] peaks at and (9.98) due to proton of amide (- CO-NH-) in compound [6], peak at and (3.5) due to proton of (CH-N=N-) in compound [6] peak at and (3.4) due to proton of (S-CH-N-) in thiazine cycle, peaks at and (3.30 -5.5) due to(12) proton of (-N –CH2 –N-) in cycles in compounds [10-13], other peaks of functional groups show in the following, table (2), fig (5-9).Other data of [(C.H.N)-analysis, physical properties ] in table (3).

 

 

 

The results of all measurements gave good evidence for synthesized compounds [2-13].

 

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Received on 30.11.2013         Modified on 20.12.2013

Accepted on 25.12.2013         © AJRC All right reserved

Asian J. Research Chem 7(1):  January 2014; Page  84-91